US20060216319A1 - Bioactive chemicals with increased activity and methods for making same - Google Patents

Bioactive chemicals with increased activity and methods for making same Download PDF

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US20060216319A1
US20060216319A1 US11/367,007 US36700706A US2006216319A1 US 20060216319 A1 US20060216319 A1 US 20060216319A1 US 36700706 A US36700706 A US 36700706A US 2006216319 A1 US2006216319 A1 US 2006216319A1
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particle size
bioactive
formulation
particles
bioactive chemical
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Andrew Chapple
Robin Taylor
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/12—Powders or granules
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/12—Powders or granules
    • A01N25/14—Powders or granules wettable

Definitions

  • This invention relates to bioactive chemicals having increased activity for use in agriculture and the pharmaceuticals industry, which are obtained by modifying the statistical properties of their formulations.
  • bioactive chemicals including pesticide and pharmaceutical formulations
  • formulations of bioactive chemicals consist of an active ingredient (AI) which is presented to a target organism or target site within an organism in particulate form, which may be either sold or liquid in capsulated or microencapsulated forms.
  • AI active ingredient
  • the efficacy of the spray cloud may be influenced by the choice of nozzle, the choice of adjuvant(s), or a combination of the two (Chapple 1993, Chapple et al. 1993a, 1994).
  • the choices of nozzle and/or adjuvant that maximize biological efficiency frequently increase off-target drift because biological efficiency and propensity for drift are both usually inversely proportional to droplet size.
  • small droplet spray clouds do not penetrate crop canopies well, so that even though the AI may be delivered in a more efficient drop size, it cannot reach the relevant parts of the crop. For this reason, AI must be applied in large droplets with concomitant waste of AI.
  • the biological efficiency of pesticides is influenced by two characteristics of the spray deposit on the foliage: deposit quantity (mass per unit area of foliage) and deposit quality (droplet size distribution and the spatial distribution of droplets on the foliage; Downer et al. 1998).
  • Deposit quantity gives a rough guide to the distribution of the active ingredient (AI) within the canopy.
  • AI active ingredient
  • a single 800 ⁇ m diameter droplet of a pesticide deposited on a leaf will not give the same biological result as the same volume deposited as 512 100 ⁇ m diameter droplets randomly or uniformly distributed on the leaf.
  • deposit quality is a key component of the application process.
  • Dose transfer is the entire process from atomization of a biocide to biological effect. It includes atomization by the nozzle, transport to the target, impaction and retention, degradation and off-target fate of AI, dose acquisition and biological effect on the target. No analytically tractable theory of dose-transfer has been derived, although components have been investigated semi-analytically and numerically (Salt & Ford 1993, Chapple & Hall 1993, Chapple et al. 1993b, 1995).
  • the present application provides new bioactive chemicals having increased bioactive activity and a method for manufacturing such materials. Specifically, the present application provides an optimum particle size or a small set of optimal particle sizes within the bioactive chemical materials in order to obtain increased activity of the active ingredient.
  • the use of an optimum particle size is desirable, since if the distribution of particle sizes can be narrowed around these optima, the amount of active ingredient (“AI”) required for a specified biological effect may be reduced.
  • AI active ingredient
  • the present application provides that a formulation comprising a bioactive material in particulate form in which at least 50% of the particles by volume or mass are in the range 0.5M to 1.5M, where M is the most biologically active particle size class (i.e. the mode), where the number of size classes is at least 12 and preferably at least 20, such that the distribution can be characterized efficiently and the mode be well defined. More specifically, it is also preferred in an alternate formulation for such bioactive chemical materials that at least 90% of the bioactive material particles by volume or mass are in the range 0.5M to 1.5M, and 50% of the particles by volume or mass are in the range 0.75M to 1.25M. In such an embodiment, where two or more particle size classes are found to increase efficacy of the AI, several fractions may be mixed together in optimum proportions determined experimentally for the AI in question.
  • the present application also provides that with respect to the improved bioactive materials, it is not always necessary to find the optimum particle size before narrowing the particle size distribution.
  • a number of narrowed particle size distributions covering a wide range of modal particle sizes may be used, all of which improve performance relative to the original particle size distribution. While not all fractions would show the same increase in efficacy when used against different targets, an increase in bioactivity would be seen, and one would simply need to determine the optimum particle size for a defined target to achieve the highest increases in bioactivity.
  • bioactive chemicals are selected by bioassaying formulations milled using conventional means, and taking the formulation that provides the best biological result (e.g., greater mortality of insects or weeds, increased crop safety margin for a selective herbicide, greater reduction in plant height for a given dose of a plant growth regulator, herbicide safener, etc. for pesticides, and greater efficacy for medicines, antibiotics, drugs, etc.).
  • Bioassays or field trial techniques for given classes of bioactive chemicals are easily found in the literature, for example the EPPO bulletins for agricultural pesticides, published by Blackwell Scientific Publications.
  • the meaning of the term “size” should include any convenient measurement of particle diameter, volume, or mass, and that the meaning of the term “class,” when used with respect to categorization of particle size, is intended to mean the interval or intervals within which observations regarding particle size fall, for example, greater than 10 to 12 micrometer diameter and greater than 12 to 14 micrometer diameter, are two adjacent particle size classes.
  • bioactive chemicals whose particles fall inside the desired range have a greater activity than those whose particles fall outside the desired range.
  • bioactive chemicals should at least include, pesticides (which includes fungicides, herbicides, insecticides and growth regulators), as well as pharmaceuticals.
  • pesticides which includes fungicides, herbicides, insecticides and growth regulators
  • the present application also discloses that for some materials, efficacy is nearly independent of the mode, and the act of narrowing the frequency distribution increases efficacy.
  • any given pesticide or medicine applied in particulate form contained a significant proportion of particles that were either less active than the most active size class or contained an excess of AI.
  • the bioactive chemical formulation has particles of size falling only within the ranges defined by the invention, the amount of AI chemical can be reduced to achieve the same result as previously obtained with a broader distribution of particle size.
  • the unwanted particles that are separated off using for example a cyclone separator system described in International Patent Application No. WO 99/42198, for a Cleaning Apparatus by Arnold & Arnold (1999), can be re-milled or treated in some other known way to obtain another material batch containing at least some particles of the desired size range and this material batch can be subjected to a further separation.
  • the frequency distribution of the conventional formulation would then be narrowed to obtain an improved bioactive chemical formulation using, for example, the cyclone separator system of the type previously described, and the proportion of AI reduction calculated.
  • the particles could be sorted using a cyclone separator of the type described in WO 99/42198, or other commercially available comparable devices.
  • An alternate approach is to use formulations where the AI is adhered to the surface of an inert particle (e.g. kaolin clay). The formulation is then fractionated into a range of narrower frequency distributions and these are tested to determine which frequency distribution shows the greatest biological effect. Then, taking the original inert carrier and fractionating the inert carrier to obtain a similar narrower frequency distribution, the loading of the AI on the optimally-sized particles can be changed to find the combination of particle size and AI concentration that gives the optimum biological efficacy.
  • an inert particle e.g. kaolin clay
  • the invention is particularly applicable to pesticide formulations (e.g. insecticides, acaricides, fungicides, herbicides, herbicide safeners, insect and plant growth regulators, and biological, both parasitic and toxic, pesticides) and especially those, where in the application stage, the pesticide can be in particulate form, such as a wettable powder (WP), suspension concentrate (EC), or pure active ingredient.
  • WP wettable powder
  • EC suspension concentrate
  • the active ingredient must either have a low solubility in the carrier liquid (for agricultural purposes, normally water, but this can be other liquids, e.g. oils) or be formulated such that the majority of the AI remains in particulate form during application.
  • the present application also provides that an improved formulation where the particle size has been narrowed such that there are fewer smaller sized particles, also contains, on average, fewer total particles.
  • One consequence of this reduction in total particle numbers is the reduction in the propensity for off-target contamination (drift) of sprayed pesticides.
  • the small droplets in the spray cloud have a reduced probability of containing any particles of the bioactive material (pesticide, growth regulator, etc.).
  • the propensity to drift is, in part, inversely related to drop size, any reduction in the quantity of the bioactive material in the smaller drops will reduce drift.
  • the invention also has applications to some semi-bioactive materials, such as in the food-processing industry where, for example, flavor is sometimes related to texture of ingredients such as chocolate, and in non-bioactive materials, for example, ceramic and metal powders such as are used in the materials and metallurgical industries.
  • FIG. 1 illustrates that particle size and concentration are nearly independent of one another and their effect on efficacy can be visualized as an ascending ridge, where the exact shape of the ridge will depend on the bioactive chemical material. Normally the relationship would be a sigmoid curve, but as shown here, it is a straight line for clarity. Deposits off the ridge are generally inefficient and wasteful, as well as potential liabilities. Bioactive material products with deposits high on the ridge require less chemical for the desired biological result.
  • FIG. 2 a is a graph showing a number distribution of particles by size for a narrowed distribution of a bendiocarb WP formulation (80% AI), with the mode at 13.7 ⁇ m compared with 11.4 ⁇ m for the original OEM formulation.
  • the relative span of the formulation was 1.84, compared with 2.90 for the original formulation.
  • FIG. 2 b is a graph showing a number distribution of particles by size for a narrowed distribution of a bendiocarb WP formulation (80% AI), with the mode at 19.7 ⁇ m compared with 11.4 ⁇ m for the original OEM formulation.
  • the relative span of the formulation was 1.81, compared with 2.90 for the original formulation.
  • FIG. 3 is a graph showing the effect of altering particle size and width of frequency distribution on the time to kill 90% (KT90) of mosquitoes ( Culex quinquefasciatus ) on ceramic tiles using the original OEM bendiocarb (Ficam WP80) formulation and small, medium, and large extended particle (“EP”) size fractions, respectively.
  • FIG. 4 is a graph showing the dose-mortality curve for southern corn rootworm ( Diabrotica undecimpunctata ) treated with fipronil (Regent WG 80) and a derived EP in a soil bioassay shows a large shift to the left and a steepening of the response curve, indicating the increased activity of the EP relative to the original OEM formulation. Note the logarithmic dose scale.
  • FIG. 5 is a graph showing the percent mortality of army worm larvae ( Spodoptera exigua ) exposed to a small EP formulation and the original OEM deltamethrin (Decis WP80) formulation over a 10 day period.
  • FIG. 6 is a graph showing the dose-mortality curve for diamondback moth ( Plutella xylostella ) treated with deltamethrin (Decis WP 80) and a derived EP applied foliarly shows a large shift to the left of the response curve, indicating the increased activity of the EP relative to the original OEM formulation. Note the logarithmic dose scale.
  • the present invention is best illustrated by describing the application of the principles disclosed here in connection with three original insecticide formulations, or bioactive chemical materials, with different modes of action (a carbamate, a fipriole, and a pyrethroid) against seven species of insect.
  • five species were challenged with one bioactive chemical.
  • the species used represent three important insect orders: Diptera (flies), Coleoptera (beetles) and Lepidoptera (moths).
  • the trial environments ranged from ceramic tile and leaf surfaces in the laboratory, to leaf surfaces in the greenhouse, to soil incorporation in the field.
  • the range of targets, substrates, and environments and the magnitude of the responses illustrate the availability of the application to various bioactive chemicals having active ingredients.
  • the following description uses these examples of insecticides, used in the fields of vector control and crop protection as a model system which would likewise be representative of all classes of pesticides, and obvious analogs with antibiotics and other pharmaceuticals.
  • the sprayer separates the physical and biological requirements of the spray cloud by placing AI only in the biologically active small droplets while retaining the large droplets required to give the cloud sufficient kinetic energy to reach the canopy.
  • This sprayer device the Double Nozzle (Taylor & Chapple 2002), of the type disclosed in U.S. Pat. No. 6,375,089, resulted from studies of the dose-transfer process.
  • the application efficiency of the Double Nozzle sprayer is at least double that of conventional delivery systems. Using the Double Nozzle, growers need use only 50% the normal quantity of AI/acre without compromising efficacy and in many cases increasing efficacy.
  • the way to produce near-monodispersed deposits using a conventional hydraulic spraying system is to formulate a water insoluble AI as solid particles (a powder) and separate out the optimum size class.
  • the narrower the size distribution of the optimum size class the more will be in the larger than optimum size class and the less wasted. Furthermore, the absence of very small particles from the optimum size class will necessarily reduce the amount of driftable AI and sub-lethal doses.
  • the term “particulates” provides a definition for the manufacturing approach to optimize pesticide particle sizes, which is also referred to herein in the product as an “extended powder” (“EP”).
  • EP extended powder
  • the underlying principle behind both the Double Nozzle and particulates technology is the concept of decoupling the biological and delivery efficiencies in spray application. Decoupling delivery and biology permits the independent optimization of delivery and biological efficiencies of both subsystems. The former does this during application by separating the physics of the delivery system from the biology of the toxin acquisition process. By contrast, the particulates technology separates the physics from the biology during the manufacturing process. This practice is limited to water insoluble active ingredients, whereas the Double Nozzle works equally well with soluble and insoluble actives. Simulations supported by the results shown in the examples below, suggest rate reductions in excess of 85% for particulates compared to 50-75% rate reductions with the Double Nozzle.
  • partates technology is used to reference the novel approach of this application, that seeks to improve the performance of water insoluble AIs by narrowing the frequency distribution of the particles present in the formulation.
  • foliar applied AIs ⁇ 5% of the AI should be soluble in the spray tank and for soil application ⁇ 1% should be soluble.
  • “particulates” is an extension of wettable powder (WP) or suspension concentrate (SC) formulations, and as such, we refer to the resulting formulation as an “extended powder” or EP formulation.
  • WP wettable powder
  • SC suspension concentrate
  • Particles which are smaller than the optimum may cause under-dosing, while particles larger cause overdosing and/or wastage.
  • the relationship between particle size (diameter) and the amount of AI present in a particle (volume or mass) follows a cube function, so that any reduction in the number of larger-than-optimum particles would lead to substantial savings in the amount of AI required for a given biological effect. Also, other effects, such as acceleration of effects, widening selectivity, and slowing the rate of resistance acquisition may also be possible.
  • the use of the spray applicators reduces application rates by at least 50% by capitalizing on the efficacy of small deposits and the necessity for large droplets in the spray cloud to achieve satisfactory delivery of AI to the target.
  • the Particulates concept takes the principle a step further. Large deposits (and therefore large droplets) of AI are clearly inefficient and wasteful as are exceedingly small deposits because they are contained in small droplets and are highly drift-prone. In addition, small deposits do not deliver enough material to the substrate for the desired level of efficacy.
  • particulate formulations reduce the application rate by lowering the frequency of the inefficient ultra-fine and very large particles that contribute to drift and waste, respectively, the density of particles in the spray tank is also reduced. This ensures that the probability of particulates being sampled by small drift-prone droplets is reduced.
  • a reduced application rate implies reduced off-target drift further reducing drift.
  • One aspect of substantially narrowing the particle size frequency distribution is the reduction in the number of particles present, through the removal of many of the small particles. It is clear that one consequence is a change in the loading of the drops most prone to drift.
  • the drops produced by the atomizing system are considered to be a sampling system, then one can easily calculate the probability that a given drop will contain no AI, using the number of particles present in the spray volume and the volume of the various drops. It is clear that if there are fewer particles, then any given drop will have a smaller chance of capturing one or more particles of AI.
  • the frequency distribution of the particles of AI remains the same; only the mode changes.
  • the cube function relationship between diameter and volume means that the relationship is non-linear.
  • the particles of AI were monodispersed (all the same size)
  • an increase by a factor of two in the particle diameter would give an eightfold reduction in number of particles, with each particle containing eight times the AI.
  • the shift of the particle size distribution from a mode of X ⁇ m diameter to 2 ⁇ m will result in even fewer particles as the larger particles in the new distribution are not only very much larger, but also very much rarer.
  • the probability is calculated for the likelihood of the various drop sizes to contain 1, 2, . . . n particles.
  • Drift results and particle sizing statistics are given in Table 1.
  • D 10 , D 50 , and D -0 are standard measurements for particle sizing and correspond to the particle diameter of the 10, 50 (median) & 90 percentiles of the particles in the sample.
  • the relative span is an estimate of the width of the distribution and is given by (D90 ⁇ D10)/D50.
  • particulates technology approach Another novel principle employed by particulates technology approach is the idea of using the atomizing system as a sampling system in which it is possible to calculate the probability that a given drop will contain no AI or AI particles of a defined size. It is clear that for a given particle size the fewer particles that are present, the smaller their chance of being captured by droplets of any defined size. By reducing the number of small particles, we reduce the chance they will be sampled by drift-prone small droplets. Thus, the particulates approach to pesticide formulation not only reduces the amount of AI required for pest control, it also reduces off-target drift. It should be noted that this drift reduction property is essentially independent of choice of nozzle—it is strictly a function of formulation. Thus, use of particulates technology is fully compatible with application by the Double Nozzle. In fact, because the Double Nozzle obtains its increased efficiency by improving delivery and particulates by improving biological efficiency by facilitating acquisition, we expect a synergistic effect when the two technologies are combined.
  • Bendiocarb was tested as three separated fractions (Small, Medium, and Large fraction EPs) of the parent Ficam WP80 (Bayer CropScience) formulation, using ceramic tiles as a surface and the mosquito vector Culex quinquefasciatus as a test organism. Four doses were tested—recommended “field” rate, half, quarter, and an eighth dose. The distributions of the original WP80 and the three fractions produced are given in Table 1.
  • the narrowed frequency distribution has a greater biological efficacy than the original WP80 formulation. Furthermore, this is independent of whether or not the mode was reduced.
  • the mode of the Medium fraction EP was the same as that of the WP80 original or parent formulation, as shown in FIG. 2 a , whereas the mode of the Large fraction EP was reduced, as shown in FIG. 2 b . In both fractions, it is the action of reducing the width of the distribution that increased the activity of the insecticide.
  • the narrowed particle size formulations had significantly faster time to knockdown of 90% (KT90), as best shown in FIG. 3 , of the mosquitoes than the original WP80 formulation. Narrowing the particle size distribution accelerated the rate of knockdown relative to the original formulation results in the same biological result with the EPs at one-quarter the dose required using the original Ficam WP80 formulation.
  • Diabrotica undecimpunctata Soil was treated with fipronil parent WG80 and EPs and Diabrotica eggs were introduced to the treated soil the day of treatment (0 DAT) and 21 days after treatment (21 DAT). Survival of Diabrotica was assessed 14 days later[0047]
  • the dose-mortality curves for Plutella xylostella are given in FIG. 6 .
  • the dose mortality parameters (DL50, LD95, and LD99) for all targets are given in Table 4. They show clear separation between the EPs and parent WP80. The dose is again in logs, so that the separation between the curves represents increases in activity of the EP of at least 4-fold.
  • the first step in using the particulates technology in the areas of pesticide and pharmaceutical production is to determine the optimum particle size of the bioactive chemical for the required biological effect. This will be achieved by challenging the target insect, weed, pathogen, or disease agent with formulations of the chemical with different-sized particles. These different-sized particle fractions will have narrowed distribution of particle sizes around selected modal sizes. The fractions will be separated by a conventional method, such as by using a cyclone separator system, tested in standardized laboratory, greenhouse and field trials, such as those described herein. Having identified one or a small number of optimum particle sizes, this information will be used in the production and formulation process of the bioactive chemical.
  • Particulates technology will be applied in practice by inserting a stage following chemical manufacturing or synthesis, which precedes product packaging. This stage will separate from the manufactured bioactive chemical, the optimized particle size identified in the preceding method. Machinery for implementing this will be similar to that used in the preceding method, but of a scale suitable for manufacturing adequate quantities of the improved bioactive chemical. The quantity deemed adequate will be determined by consideration of the size of the market and the volume of material required to serve that market.
  • particulates-formulated active ingredients have increased efficacy relative to their original or OEM product formulations.
  • Es particulates-formulated active ingredients
  • FIG. 4 shows a steepening of the dose-mortality curve and/or a shifting, as seen in FIG. 6 , of the dose-mortality curve to the left, relative to the original product formulation.
  • These changes in the dose-mortality relationships brought about by optimizing the particle size distributions act in two ways, as an acceleration of the rate at which a given result can be obtained and as a true reduction in the amount of active ingredient required for a given biological effect.
  • Dose-mortality statistics for fipronil show a nearly five-fold decrease in dose of the EP Small fraction required to kill 90-99% of southern corn rootworm ( Diabrotica undecimpunctata ) in a soil bioassay.
  • Dose-mortality statistics for foliar applications of deltamethrin (Decis WP80) against three moths ( Plutella xylostella , Spodoptera frugiperda , and Heliothis armigera ) and a beetle ( Phaedon cochleariae ) show large increases in activity of the extended powder (EP Small) over the parent WP80.
  • Target Form LD50 LD90 LD95 LD99 D Target Form LD50 LD90 LD95 LD99 D.

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1518568A (en) * 1975-11-19 1978-07-19 Bayer Ag Process for the preparation of concentrated suspensions of pesticides
US6541426B1 (en) * 1999-06-18 2003-04-01 Rohm And Haas Company Method to produce pesticide suspension concentrates
US20030083826A1 (en) * 2001-04-19 2003-05-01 Moshe Danny S. Method for generating intra-particle crystallographic parameter maps and histograms of a chemically pure crystalline particulate substance

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DK570987A (da) * 1986-12-01 1988-06-02 Hoffmann La Roche Oxadiazol-, thiadiazol- og triazolforbindelser
DE10032137B4 (de) * 2000-07-01 2009-04-02 Allessachemie Gmbh Verfahren zur Herstellung von Phenothiazin-Granulat mit verbesserten Eigenschaften

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1518568A (en) * 1975-11-19 1978-07-19 Bayer Ag Process for the preparation of concentrated suspensions of pesticides
US6541426B1 (en) * 1999-06-18 2003-04-01 Rohm And Haas Company Method to produce pesticide suspension concentrates
US20030083826A1 (en) * 2001-04-19 2003-05-01 Moshe Danny S. Method for generating intra-particle crystallographic parameter maps and histograms of a chemically pure crystalline particulate substance

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